Provided are: forming an oxycarbonitride film, an oxycarbide film or an oxide film on a substrate by alternately performing a specific number of times: forming a first layer containing the specific element, nitrogen and carbon, on the substrate, by alternately performing a specific number of times, supplying a first source containing the specific element and a halogen-group to the substrate in a processing chamber, and supplying a second source containing the specific element and an amino-group to the substrate in the processing chamber; and forming a second layer by oxidizing the first layer by supplying an oxygen-containing gas, and an oxygen-containing gas and a hydrogen-containing gas to the substrate in the processing chamber.Related Terms:SemiconductorHydrogenNitrogenSemiconductor Device

TECHNICAL FIELD

The present invention relates to a method of manufacturing a semiconductor device including a step of forming a thin film on a substrate, a substrate processing method and a substrate processing apparatus.

DESCRIPTION OF RELATED ART

A high resistance to hydrogen fluoride (HF) and low dielectric constant are required for a thin film such as an insulating film constituting a side wall spacer (SWS) of a gate electrode. Therefore, a silicon carbonitride film (SiCN film) in which carbon (C) is added to a silicon nitride film (SiN film), or a silicon oxycarbonitride film (SiOCN film), etc., in which oxygen (O) is further added thereto, is used as the insulating film. A high step coverage characteristic is requested for these insulating films, and therefore these insulating films are formed in many cases not by a general CVD (Chemical Vapor Deposition) method of simultaneously supplying processing gases, but an alternately supplying method such as ALD (Atomic Layer Deposition) method, etc., of alternately supplying processing gases.

SUMMARY

OF THE INVENTION

Problem to be Solved by the Invention

In order to further improve the resistance to HF, or further reducing the dielectric constant of the insulating films such as the SiCN film and the SiOCN film, it is effective to reduce a nitrogen concentration, or increase a carbon concentration, or increase an oxygen concentration in a film. However, in a conventional alternately supplying method, it is difficult to form a film with the carbon concentration exceeding the nitrogen concentration for example. Further, a lower film formation temperature is requested for forming the insulating film constituting the side wall spacer, etc. However, the film formation temperature in the conventional alternately supplying method is around 600° C., and it is difficult to form the thin film such as the above-mentioned insulating film, etc., in a low temperature zone of 550° C. or less for example.

Accordingly, an object of the present invention is to provide a method of manufacturing a semiconductor device, a substrate processing method, and a substrate processing apparatus, capable of forming an excellent thin film in a low temperature zone.

Means for Solving the Problem

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, including:

forming an oxycarbonitride film, an oxycarbide film or an oxide film containing a specific element on a substrate by alternately performing a specific number of times:

forming a first layer containing the specific element, nitrogen and carbon, on the substrate, by alternately performing a specific number of times, supplying a first source containing the specific element and a halogen-group to the substrate in a processing chamber, and supplying a second source containing the specific element and an amino-group to the substrate in the processing chamber; and

forming a second layer by oxidizing the first layer by supplying an oxygen-containing gas, or an oxygen-containing gas and a hydrogen-containing gas to the substrate in the processing chamber.

According to other aspect of the present invention, there is provided a substrate processing method, including:

forming an oxycarbonitride film, an oxycarbide film or an oxide film containing a specific element on a substrate by alternately performing a specific number of times:

forming a first layer containing the specific element, nitrogen and carbon, on the substrate, by alternately performing a specific number of times, supplying a first source containing the specific element and a halogen-group to the substrate in a processing chamber, and supplying a second source containing the specific element and an amino-group to the substrate in the processing chamber; and

forming a second layer by oxidizing the first layer by supplying an oxygen-containing gas, or an oxygen-containing gas and a hydrogen-containing gas to the substrate in the processing chamber.

According to further other aspect of the present invention, there is provided a substrate processing apparatus, including:

a processing chamber configured to house a substrate;

a first source supply system configured to supply a first source containing a specific element and a halogen-group, to a substrate in the processing chamber;

a second source supply system configured to supply a second source containing the specific element and an amino-group, to a substrate in the processing chamber:

a reaction gas supply system configured to supply an oxygen-containing gas, or an oxygen-containing gas and a hydrogen-containing gas, to a substrate in the processing chamber; and

a control part configured to control the first source supply system, the second source supply system and the reaction gas supply system, so that an oxycarbonitride film, an oxycarbide film or an oxide film containing the specific element, is formed on a substrate, by alternately performing a specific number of times, a process of forming a first layer containing the specific element, nitrogen and carbon on the substrate by alternately performing a specific number of times a process of supplying the first source to the substrate in the processing chamber, and a process of supplying the second source to the substrate in the processing chamber; and a process of forming a second layer by oxidizing the first layer by supplying the oxygen-containing gas, or the oxygen-containing gas and the hydrogen-containing gas to the substrate in the processing chamber.

Advantage of the Invention

According to the present invention, there are provided a method of manufacturing a semiconductor device, a substrate processing method, and a substrate processing apparatus, capable of forming an excellent thin film in a low temperature zone.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic block diagram of a vertical-type processing furnace of a substrate processing apparatus suitably used in this embodiment, and a view showing a processing furnace portion in a vertical sectional view.

FIG. 2 is a schematic block diagram of the vertical-type processing furnace of the substrate processing apparatus suitably used in this embodiment, and a view showing the processing furnace portion taken along the line A-A of FIG. 1.

FIG. 3 is a view showing a film formation flow in a first sequence of this embodiment.

FIG. 4 is a view showing the film formation flow in a second sequence of this embodiment.

FIG. 5 is a view showing the timing of supplying gas in the first sequence of this embodiment.

FIG. 6 is a view showing the timing of supplying gas in the second sequence of this embodiment.

FIG. 7 is a view showing the timing of supplying gas in a third sequence of this embodiment.

FIG. 8 is a view showing the timing of supplying gas in a fourth sequence of this embodiment.

FIG. 9 is a view showing the timing of supplying gas in other embodiment.

FIG. 10 is a view showing the timing of supplying gas in other embodiment.

FIG. 11 is a graph chart showing a measurement result of XRF according to example 1 of the present invention.

FIG. 12 is a graph chart showing the measurement result of an XPS spectrum according to example 2 of the present invention.

FIG. 13 is a graph chart showing the measurement result of an etching rate according to example 2 of the present invention.

FIG. 14 is a graph chart showing the measurement result of a dielectric constant according to example 2 of the present invention.

FIG. 15 is a graph chart showing the measurement result of O-concentration, C-concentration, and N-concentration according to example 3 of the present invention.

FIG. 16 is a schematic block diagram of a controller of a substrate processing apparatus suitably used in this embodiment.

MODES FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described hereafter, based on the drawings.

FIG. 1 is a schematic block diagram of a vertical-type processing furnace of a substrate processing apparatus suitably used in this embodiment, and shows a processing furnace 202 portion in a vertical sectional view, and FIG. 2 is a schematic block diagram of the vertical-type processing furnace suitably used in this embodiment, and a view showing the processing furnace portion taken along the line A-A of FIG. 1

As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating unit (heating mechanism). The heater 207 has a cylindrical shape, and is vertically installed on a heater base (not shown) as a holding plate by being supported thereby. The heater 207 also functions as an activation mechanism of activating a gas by heat as will be described later. The heater 207 also functions as an activation mechanism of activating a gas by heat as will be described later.

A reaction tube 203 constituting a reaction vessel (processing vessel) is disposed inside of the heater 207 concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), etc., for example, and is formed into a cylindrical shape, with an upper end closed and a lower end opened. A processing chamber 201 is formed in a cylinder hollow part of the reaction tube 203, so that wafers 200 being substrates, can be stored by a boat in a state of being vertically arranged in multiple stages in a horizontal posture.

A first nozzle 249a, a second nozzle 249b, and a third nozzle 249c are provided in the processing chamber 201 so as to pass through a lower part of the reaction tube 203. A first gas supply tube 232a, a second gas supply tube 232b, and a third gas supply tube 232c are respectively connected to the first nozzle 249a, the second nozzle 249b, and the third nozzle 249c. Further, a fourth gas supply tube 232d is connected to the third gas supply tube 232c. Thus, three nozzles 249a, 249b, 249c, and four gas supply tubes 232a, 232b, 232c, 232d are provided on the reaction tube 203, so that a plurality of kinds of gases, four kinds of gases here, can be supplied into the processing chamber 201.

A metal manifold for supporting the reaction tube 203 may be provided in a lower part of the reaction tube 203, and each nozzle may be provided so as to pass through a side wall of the metal manifold. In this case, an exhaust tube 231 described later may further be provided in this metal manifold. In this case as well, the exhaust tube 231 may be provided not on the metal manifold, but in the lower part of the reaction tube 203. Thus, a furnace throat portion of the processing furnace 202 may be made of metal, and a nozzle, etc., may be attached to the metal furnace throat portion.

A mass flow controller (MFC) 241a being a flow rate control unit (flow rate control part) and a valve 243a being an open/close valve are provided on the first gas supply tube 232a sequentially from an upstream direction. Further, a first inert gas supply tube 232e is connected to a downstream side of the valve 243a of the first gas supply tube 232a. A mass flow controller 241e being a flow rate control unit (flow rate control part), and a valve 243e being an open/close valve are provided on the first inert gas supply tube 232e sequentially from the upstream direction. Further, the above-mentioned first nozzle 249a is connected to a tip part of the first gas supply tube 232a. The first nozzle 249a is provided in an arc-shaped space between an inner wall of the reaction tube 203 and the wafers 200, extending from a lower part to an upper part of the inner wall of the reaction tube 203, so as to rise toward an upper part of a stacking direction of the wafers 200. Namely, the first nozzle 249a is provided in a region horizontally surrounding a wafer arrangement region in which the wafers 200 are arranged, at a side part of the wafer arrangement region, along the wafer arrangement region. The first nozzle 249a is formed as an L-shaped long nozzle, with its horizontal part provided so as to pass through a lower side wall of the reaction tube 203, and with its vertical part provided so as to rise from at least one end side toward the other end side of the wafer arrangement region. Gas supply holes 250a for supplying a gas, are provided on a side face of the first nozzle 249a. Each gas supply hole 250a is opened to face a center of the reaction tube 203, so that the gas can be supplied toward the wafers 200. A plurality of gas supply holes 250a are provided extending from a lower part to an upper part of the reaction tube 203, each of them having the same opening area and provided at the same opening pitch. A first gas supply system is mainly constituted of the first gas supply tube 232a, the mass flow controller 241a, the valve 243a, and the first nozzle 249a. Also, a first inert gas supply system is mainly constituted of the first inert gas supply tube 232e, the mass flow controller 241e, and the valve 243e.

A mass flow controller (MFC) 241b being a flow rate control unit (flow rate control part), and a valve 243b being an open/close valve, are provided on the second gas supply tube 232b, sequentially from the upstream direction. Further, a second inert gas supply tube 232f is connected to a downstream side of the valve 243b of the second gas supply tube 232b. A mass flow controller 241f, and a valve 243f being the open/close valve are provided on the second inert gas supply tube 232f sequentially from the upstream direction. Further, the second nozzle 249b is connected to an edge portion of the second gas supply tube 232b. The second nozzle 249b is provided in the arc-shaped space between the inner wall of the reaction tube 203 and the wafers 200, extending from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise toward the upper part of the stacking direction of the wafers 200. Namely, the second nozzle 249b is provided in the region horizontally surrounding the wafer arrangement region, at the side part of the wafer arrangement region in which the wafers 200 are arranged, along the wafer arrangement region. The second nozzle 249b is formed as an L-shaped long nozzle, with its horizontal part provided so as to pass through the lower side wall of the reaction tube 203, and with its vertical part provided so as to rise from at least one end side toward the other end side of the wafer arrangement region. Gas supply holes 250b for supplying a gas, are provided on a side face of the second nozzle 249b. Each gas supply hole 250b is opened to face the center of the reaction tube 203, so that the gas can be supplied toward the wafers 200. A plurality of gas supply holes 250b are provided extending from the lower part to the upper part of the reaction tube 203, each of them having the same opening area and provided at the same opening pitch. A second gas supply system is mainly constituted of the second gas supply tube 232b, the mass flow controller 241b, the valve 243b, and the second nozzle 249b. Also, a second inert gas supply system is mainly constituted of the second inert gas supply tube 232f, the mass flow controller 241f, and the valve 243f.

A mass flow controller (MFC) 241c being a flow rate control unit (flow rate control part), and a valve 243c being an open/close valve, are provided on the second gas supply tube 232c, sequentially from the upstream direction. Further, a fourth gas supply tube 232d is connected to a downstream side of the valve 243c of the third gas supply tube 232c. A mass flow controller 241d, and a valve 243d being the open/close valve are provided on the fourth gas supply tube 232d sequentially from the upstream direction. Further, a third inert gas supply tube 232g is connected to the downstream side of a connection part connected to the fourth gas supply tube 232d on the third gas supply tube 232c. A mass flow controller 241g being the flow rate control unit (flow rate control part), and a valve 243g being the open/close valve, are provided on the third inert gas supply tube 232g. Further, the above-mentioned third nozzle 249c is connected to the edge portion of the third gas supply tube 232c. The third nozzle 249c is provided in the arc-shaped space between the inner wall of the reaction tube 203 and the wafers 200, extending from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise toward the upper part of the stacking direction of the wafers 200. Namely, the second nozzle 249c is provided in the region horizontally surrounding the wafer arrangement region in which the wafers 200 are arranged, at the side part of the wafer arrangement region, along the wafer arrangement region. The third nozzle 249c is formed as the L-shaped long nozzle, with its horizontal part provided so as to pass through the lower side wall of the reaction tube 203, and with its vertical part provided so as to rise from at least one end side toward the other end side of the wafer arrangement region. Gas supply holes 250c for supplying gas, are provided on a side face of the third nozzle 249c. Each gas supply hole 250c is opened to face the center of the reaction tube 203, so that the gas can be supplied toward the wafers 200. A plurality of gas supply holes 250c are provided extending from the lower part to the upper part of the reaction tube 203, each of them having the same opening area and provided at the same opening pitch. A third gas supply system is mainly constituted of the third gas supply tube 232c, the mass flow controller 241c, the valve 243c, and the third nozzle 249c. Also, a fourth gas supply system is mainly constituted of the fourth gas supply tube 232d, the mass flow controller 241d, the valve 243d, and the third nozzle 249c. Further, a third inert gas supply system is mainly constituted of the third inert gas supply tube 232g, the mass flow controller 241g, and the valve 243g.

Thus, in the method of supplying gas according to this embodiment, gas is transferred through nozzles 249a, 249b, 249c disposed in the arc-shaped vertically long space defined by the inner wall of the reaction tube 203 and edge portions of the plurality of stacked wafers 200, and the gas is sprayed into the reaction tube 203 for the first time in the vicinity of the wafers 200 from the gas supply holes 250a, 250b, 250c which are opened on the nozzles 249a, 249b, 240c respectively, so that the gas flows mainly in parallel to the surface of the wafers 200, namely in a horizontal direction. With this structure, the following effect can be obtained. Namely, the gas can be uniformly supplied to each wafer 200, and a film thickness of the thin film formed on each wafer 200 can be equalized. The gas flowing on the surface of the wafers 200, namely a remained gas after reaction flows toward an exhaust port, namely in a direction of the exhaust tube 231 described later. However, the direction of the flow of such a remained gas is suitably specified by a position of the exhaust port and is not limited to the vertical direction.

A chlorosilane-based source gas being a first source gas containing at least a silicon (Si) element and a chloro-group, is supplied from the first gas supply tube 232a into the processing chamber 201 through the mass flow controller 241a, the valve 243a, and the first nozzle 249a, as a first source containing a specific element and a halogen-group. Wherein, the chlorosilane-based source means a silane-based source having the chloro-group, and means the source containing at least silicon (Si) and chlorine (Cl). As the chlorosilane-based source gas, for example, a hexachlorodisilane (Si2Cl6, abbreviated as HCDS) gas can be used. When a liquid source in a liquid state under normal temperature and pressure like the HCDS is used, the liquid source is vaporized by a vaporization system such as a vaporizer or a bubbler, etc., and is supplied as the source gas (HCDS gas).

As a second source containing the specific element and an amino-group (amine-group), an aminosilane-based source gas being the second source gas containing at least silicon (Si) element and the amino-group, is supplied into the processing chamber 201 from the second gas supply tube 232b through the mass flow controller 241b, the valve 243b, and the second nozzle 249b. Wherein, the aminosilane-based source means a silane-based source having the amino-group (this is also the silane-based source containing a methyl-group and an ethyl group), which is the source containing at least silicon (Si), nitrogen (N) and carbon (C). As the aminosilane-based source gas, for example trisdimethylaminosilane (Si[N(CH3)2]3H, abbreviated as 3DMAS) gas can be used. When using the liquid source in the liquid state at normal temperature and pressure like 3DMAS, the liquid source is vaporized by the vaporization system such as the vaporizer and the bubbler, etc., and is supplied as the source gas (3DMAS gas).

For example, the gas containing oxygen (O) (oxygen-containing gas) is supplied into the processing chamber 201 from the third gas supply tube 232c through the mass flow controller 241c, the valve 243c, and the third nozzle 249c. For example, an oxygen (O2) gas can be used as the oxygen-containing gas.

For example, the gas containing hydrogen (H) (hydrogen-containing gas) is supplied into the processing chamber 201 from the fourth gas supply tube 232d through the mass flow controller 241d, the valve 243d, and the third gas supply tube 232c, and the third nozzle 249c. For example, a hydrogen (H2) gas can be used as the hydrogen-containing gas.

For example, when the gas like the above-mentioned gas is flowed from each gas supply tube, a first source supply system for supplying the first source containing the specific element and the halogen-group, namely, a chlorosilane-based source gas supply system as the first source gas supply system is constituted by the first gas supply system. Further, a second source supply system for supplying the second source containing the specific element and the amino-group, namely an aminosilane-based source gas supply system as the second source gas supply system is constituted by the second gas supply system. The chlorosilane-based source gas supply system and the aminosilane-based source gas supply system are also simply called a chlorosilane-based source supply system, and an aminosilane-based source supply system respectively. Further, an oxygen-containing gas supply system is constituted by the third gas supply system. Also, a hydrogen-containing gas supply system is constituted by the fourth gas supply system. When the oxygen-containing gas and the hydrogen-containing gas are generally called a reaction gas, a reaction gas supply system is constituted by the oxygen-containing gas supply system and the hydrogen-containing gas supply system.

The exhaust tube 231 for exhausting the atmosphere in the processing chamber 201 is provided on the reaction tube 203. As shown in FIG. 2, the exhaust tube 231 is provided on a side opposed to the side where the gas supply holes 250a of the first nozzle 249a and the gas supply holes 250b of the second nozzle 249b of the reaction tube 203 are provided, namely on the opposite side to the gas supply holes 250a, 250b with the wafers 200 interposed between them, in cross-sectional view. Further, as shown in FIG. 1 in a vertical sectional view, the exhaust tube 231 is provided below the part where the gas supply holes 250a, 250b are provided. With this structure, the gas supplied in the vicinity of the wafers 200 in the processing chamber 201 from the gas supply holes 250a, 250b, flows in the horizontal direction, namely in parallel to the surface of the wafers 200, and thereafter flows downward and is exhausted from the exhaust tube 231. As described above, the gas flows mainly in the horizontal direction in the processing chamber 201.

A vacuum pump 246 being a vacuum exhaust device is connected to the exhaust tube 231, through a pressure sensor 245 being a pressure detector (pressure detection part) for detecting a pressure in the processing chamber 201, and an APC (Auto Pressure Controller) valve 244 being a pressure adjuster (pressure adjustment part). An exhaust system is mainly constituted of the exhaust tube 231, the APC valve 244, and the pressure sensor 245. It is also acceptable that the vacuum pump 246 is included in the exhaust system. The vacuum pump 246 is configured to perform vacuum-exhaust and stop of vacuum-exhaust of the inside of the processing chamber 201 by opening/closing the valve while operating the vacuum pump 246, and is also configured to adjust the pressure in the processing chamber 201 by adjusting a valve degree while operating the vacuum pump 246. The exhaust system is configured to vacuum-exhaust the inside of the processing chamber 201 so as to be a specific pressure (vacuum degree) by adjusting the opening degree of the APC valve 244 based on pressure information detected by the pressure sensor 245 while operating the vacuum pump 246.

A seal cap 219 as a furnace throat lid member capable of air-tightly closing a lower end opening of the reaction tube 203, is provided in the lower part of the reaction tube 203. The seal cap 219 is configured to abut on the lower end of the reaction tube 203 from a vertical lower side. The seal cap 219 is made of metal such as stainless, etc., and is formed into a disc shape. An O-ring 220 as a seal member abutted on the lower end of the reaction tube 203, is provided on an upper surface of the seal cap 219. A rotation mechanism 267 for rotating a boat 217 as a substrate holding tool described later, is installed on an opposite side of the processing chamber 201 across the seal cap 129. A rotary shaft 255 of the rotation mechanism 267 is passed through the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically elevated by a boat elevator 115 as an elevation mechanism vertically installed outside of the reaction tube 203. The boat elevator 115 is configured to load and unload the boat 217 into/from the processing chamber 201 by elevating the seal cap 219. Namely, the boat elevator 115 is configured as a transferring device (transferring mechanism) for transferring the boat 217 namely the wafers 200 into/from the processing chamber 201.

The boat 217 as a substrate supporter, is made of a heat-resistant material such as quartz and silicon carbide, etc., and is configured to support a plurality of wafers 200 in a horizontal posture, with centers thereof aligned, so as to be arranged in multiple stages. A heat insulating member 218 made of the heat-resistant material such as quartz and silicon carbide, etc., is provided in a lower part of the boat 217, so that a heat from the heater 207 is hardly transmitted to the seal cap 219 side. The heat-insulating member 218 may also be configured by a plurality of heat-insulating plates made of the heat-resistant material such as quartz and silicon carbide, etc., and a heat-insulating plate holder for supporting these heat-insulting plates in a horizontal posture in multiple stages.

A temperature sensor 263 as a temperature detector, is installed in the reaction tube 203, and by adjusting a power supply state to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 is set to have a desired temperature distribution. Similarly to the nozzles 249a and 249b, 249c, the temperature sensor 263 is formed into the L-shape, and is provided along the inner wall of the reaction tube 203.

As shown in FIG. 16, the controller 121 being the control part (control unit), is configured as a computer including CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a memory device 121c, and I/O port 121d. The RAM 121b, the memory device 121c, and the I/O port 121d are configured to perform data exchange with CPU 121a via an internal bus 121e. An input/output device 122 configured as a touch panel, etc., is connected to the controller 121.

The memory device 121c includes a flash memory, and HDD (Hard Disk Drive), etc., for example. A control program for controlling an operation of the substrate processing apparatus, and a process recipe, etc., indicating a procedure and a condition, etc., of substrate processing as will be descried later, are readably stored in the memory device 121c. The process recipe is a combination of recipes, so that each procedure in a substrate processing step described later is executed by the controller 121 to obtain a specific result, and functions as a program. The process recipe and the control program, etc., are generally simply called a program. When using the term of a program in this specification, the program means a case of including the process recipe alone, a case of including a control program alone, or a case including the both cases. The RAM 121b is configured as a memory area (work area) in which the program and data, etc., read by the CPU 121a are temporarily stored.

The CPU 121a is configured to read and execute the control program from the memory device 121c, and is configured to read the process recipe from the memory device 121c according to an input, etc., of an operation command from the input/output device 122. Then, the CPU 121a is configured to control a flow rate adjustment operation of each kind of gas by the mass flow controllers 241a, 241b, 241c, 241d, 241e, 241f, 241g, an open/close operation of the valves 243a, 243b, 243c, 243d, 243e, 243g, an open/close operation of the APC valve 244, a pressure adjustment operation based on the pressure sensor 245 by the APC valve 244, a temperature adjustment operation of the heater 207 based on the temperature sensor 263, start/stop of the vacuum pump 246, a rotation speed adjustment operation of the rotation mechanism 267, and an elevating operation of the boat 217 by the boat elevator 115.

The controller 121 may be configured not only as a dedicated computer, but also as a general-purpose computer. For example, an external memory device storing the above-mentioned program (for example, a magnetic tape, a magnetic disc such as a flexible disc and a hard disc, etc., an optical disc such as CD and DVD, etc., an optical magnetic disc such as MO, etc., and a semiconductor memory such as a USB memory and a memory card, etc.) 123, is prepared, and by using the external memory device 123, the program is installed in the general-purpose computer, to thereby constitute the controller 121 according to this embodiment. A unit for supplying the program to the computer, is not limited to a case of supplying it through the recording medium 123. For example, a communication unit such as Internet and a dedicated line, etc., may be used, to thereby supply the program not through the external memory device 123. The memory device 121c and the external memory device 123 are configured as computer-readable recording media. They are also generally simply called recording media. When using the term of the recording media in this specification, the recording media mean a case of including the memory device 121c alone, a case of including the external memory device 123 alone, or a case of including the both cases.

Next, explanation is given for an example of a sequence of forming an insulating film on the substrate as one step of the manufacturing step of a semiconductor device using the processing furnace of the above-mentioned substrate processing apparatus. In the explanation given hereafter, an operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

Explanation is given for a conventional CVD (Chemical Vapor Deposition) method and an ALD (Atomic Layer Deposition) method. For example, in the case of the CVD method, a plurality of kinds of gases containing a plurality of elements constituting a film to be formed, are simultaneously supplied, and in the case of the ALD method, the plurality of kinds of gases containing a plurality of elements constituting the film to be formed, are alternately supplied. Then, a SiO2 film and a Si3N4 film are formed by controlling supply conditions such as a gas supply flow rate, a gas supply time, and a processing temperature. In these techniques, for example the supply conditions are controlled so that a composition ratio of the film is O/Si≈2 which is a stoichiometric composition when the SiO2 film is formed, and so that the composition ratio of the film is N/Si≈33 which is the stoichiometric composition when the Si3N4 film is formed.

Meanwhile, according to an embodiment of the present invention, the supply conditions are controlled so that the composition ratio of the film to be formed is the stoichiometric composition, or is a specific composition ratio different from the stoichiometric composition. For example, the supply conditions are controlled so that at least one element of the plurality of elements constituting the film to be formed, is more excessive to the stoichiometric composition, than other element. Explanation is given hereafter for a ratio of the plurality of elements constituting the film to be formed, namely an example of the sequence of forming a film while controlling the composition ratio of the film.

In a film formation sequence of this embodiment, a silicon oxycarbonitride film or a silicon oxycarbide film having a specific composition and a specific film thickness, is formed on a wafer 200 by alternately performing:

forming a first layer containing silicon, nitrogen and carbon on the wafer 200 by alternately supplying a chlorosilane-based source and an aminosilane-based source, to the wafer 200 in a processing chamber 201; and

forming a silicon oxycarbonitride layer or a silicon oxycarbide layer as a second layer by oxidizing the first layer by supplying an oxygen-containing gas to the wafer 200 in the processing chamber 201.

Here, “by alternately supplying a chlorosilane-based source and an aminosilane-based source, . . . ” includes both of the case of performing one set of supplying one of the sources of the chlorosilane-based source and the aminosilane-based source, and thereafter supplying the other source, with this cycle as one set, and the case of repeating this set multiple numbers of times, and means that this set is performed once or more (a specific number of times). The case of performing this set once, corresponds to the first sequence described later, and the case of repeating this set multiple numbers of times, corresponds to the second sequence described later.

Further, “by alternately performing: forming a first layer, and forming a second layer . . . ” includes both cases of performing a cycle of forming the first layer and forming the second layer once, with this sequence as one cycle, and repeating this cycle multiple numbers of times, and means that this cycle is performed once or more (the specific number of times).

(First Sequence)

First, the first sequence of this embodiment will be described.

FIG. 3 is a view showing a film formation flow in the first sequence of this embodiment. FIG. 5 is a view showing a timing of supplying gas in the first sequence of this embodiment.

In the first sequence of this embodiment, a silicon oxycarbonitride film or a silicon oxycarbide film having a specific composition and a specific film thickness, is formed on a wafer 200 by alternately performing:

forming a first layer containing silicon, nitrogen and carbon on the wafer 200 by supplying one of the sources of a chlorosilane-based source and an aminosilane-based source to the wafer 200 in a processing chamber, and thereafter supplying other source thereto; and

forming a silicon oxycarbonitride layer or a silicon oxycarbide layer as a second layer by oxidizing the first layer by supplying an oxygen-containing gas to the wafer 200 in the processing chamber 201.

FIG. 3 and FIG. 5 show an example of supplying the chlorosilane-based source and thereafter supplying the aminosilane-based source to the wafer 200 in the processing chamber 201, namely supplying the chlorosilane-based source prior to the aminosilane-based source.

The first sequence of this embodiment will be specifically described hereafter. Here, explanation is given for an example of forming the silicon oxycarbonitride film (SiOCN film) or the silicon oxycarbide film (SiOC film) on the wafer 200 as the insulating film, based on the film formation flow of FIG. 3, and the sequence of FIG. 5, using the HCDS gas as the chlorosilane-based source gas, and the 3DMAS gas as the aminosialne-based source gas, and the O2 gas as the oxygen-containing gas.

When a plurality of wafers 200 are charged into the boat 217 (wafer charge), as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200, are lifted by the boat elevator 115 and are loaded into the processing chamber 201 (boat load). In this state, the seal cap 219 is set in a state of sealing the lower end of the reaction tube 203 through the O-ring 220.

The inside of the processing chamber 201 is vacuum-exhausted by the vacuum pump 246 so as to be set in a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and based on the measured pressure information, the APC valve 244 is feedback-controlled (pressure adjustment). The state of the vacuum pump 246 is always set in an operation state, at least until the processing to the wafer 200 is completed. Further, the inside of the processing chamber 201 is heated by the heater 207 so as to be set at a desired temperature. At this time, the power supply state to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so as to have a desired temperature distribution (temperature adjustment). Heating the inside of the processing chamber 201 by the heater 207, is continuously performed, at least until the processing to the wafer 200 is completed. Subsequently, rotations of the boat 217 and the wafer 200 are started by the rotation mechanism 267. The rotations of the boat 217 and the wafer 200 by the rotation mechanism 267 are continuously performed, at least until the processing to the wafer 200 is completed.

(Step of Forming the Silicon Oxycarbonitride Film or the Silicon Oxycarbide Film)

Thereafter, following three steps, namely, steps 1 to 3 are sequentially executed.

[Step 1]

The valve 243a of the first gas supply tube 232a is opened, to thereby flow the HCDS gas to the first gas supply tube 232a. The HCDS gas flows in the first gas supply tube 232a, with the flow rate adjusted by the mass flow controller 241a. The HCDS gas with the flow rate adjusted, is supplied into the processing chamber 201 from the gas supply holes 250a of the first nozzle 249a, and is exhausted from the exhaust tube 231. At this time, the HCDS gas is supplied to the wafer 200 (supply of the HCDS gas). Simultaneously at this time, the valve 243e is opened, to thereby flow the inert gas such as the N2 gas, etc., into the inert gas supply tube 232e. The N2 gas flows into the inert gas supply tube 232e, with the flow rate adjusted by the mass flow controller 241e. The N2 gas with the flow rate adjusted, is supplied into the processing chamber 201 together with the HCDS gas, and is exhausted from the exhaust tube 231. At this time, in order to prevent the invasion of the HCDS gas into the second nozzle 249b and the third nozzle 249c, the valves 243f, 243g are opened, to thereby flow the N2 gas into the second inert gas supply tube 232f and the third inert gas supply tube 232g. The N2 gas is supplied into the processing chamber 201 through the second nozzle 249b, the third gas supply tube 232c, the second nozzle 249b, and the third nozzle 249c, and is exhausted from the exhaust tube 231.

At this time, the APC valve 244 is properly adjusted, to thereby set the pressure in the processing chamber 201 to the pressure in the range of 1 to 13300 Pa and preferably set to the pressure in the range of 20 to 1330 Pa for example. The supply flow rate of the HCDS gas controlled by the mass flow controller 241a is set to the supply flow rate in the range of 1 to 1000 sccm for example. The supply flow rate of the N2 gas controlled by the mass flow controllers 241e, 241f, 241g is set to the supply flow rate in the range of 100 to 10000 sccm for example. The time for supplying the HCDS gas to the wafer 200, namely a gas supply time (irradiation time) is set to the time in the range of 1 to 120 seconds, and preferably 1 to 60 seconds for example. The temperature of the heater 207 at this time is set so that the temperature of the wafer 200 is set to the temperature for example in the range of 250 to 700° C., preferably 350 to 650° C., and more preferably 350 to 600° C. When the temperature of the wafer 200 is less than 250° C., the HCDS is hardly chemically adsorbed on the wafer 200, and a practical film formation rate cannot be obtained in some cases. This can be solved by setting the temperature of the wafer 200 to 250° C. or more. Also, by setting the temperature of the wafer 200 to 350° C. or more, the HCDS can be more sufficiently adsorbed on the wafer 200, and a more sufficient film formation rate can be obtained. Further, when the temperature of the wafer 200 exceeds 700° C., the CVD reaction occurs strongly (a vapor phase reaction is dominant), to thereby easily deteriorate the uniformity of the film thickness, and control of the film thickness becomes difficult. By setting the temperature of the wafer 200 to 700° C. or less, the deterioration of the uniformity of the film thickness can be suppressed, and the control of the film thickness can be achieved. Particularly, by setting the temperature of the wafer 200 to 650° C. or less, or further 600° C. or less, a surface reaction becomes dominant, thus easily securing the uniformity of the film thickness and easily facilitating the control of the film thickness. Therefore the temperature of the wafer 200 is set to the temperature in the range of 250 to 700° C., preferably 300 to 650° C., and further preferably 350 to 600° C.

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